Amorphous Se species anchored into enclosed carbon skeleton bridged by chemical bonding toward advanced K-Se batteries

Potassium-selenium(K-Se)batteries have attracted significant attention as one of the most promising alternatives of lithium-ion storage systems owing to high energy density and low cost.In the design of Se-based cathode materials,however,the low utilization rate of active Se and the rapid dissolution of polyselenides seriously weaken the capacity and cycle stability.Therefore,how to make full use of Se species without loss during the charge and discharge process is the key to design high-performance Se-based cathode.In this paper,a 3 D"water cube"-like Se/C hybrid(denoted as Se-O-PCS)is constructed with the assistance of Na_(2)CO_(3) templates.Thanks to the abundant carbonate groups(CO_(3)^(2-))originated from the Na_(2)CO_(3) templates,the molten Se species are firmly anchored into the pore of carbon skeleton by strong C-O-Se bonding.Thus,this unique Se-O-PCS model not only improves the utilization of active Se species,but also can reduce the contact with the electrolyte to inhibit the shuttle effect of polyselenides.Moreover,flexible carbon skeleton gives Se-O-PCS hybrid a good electrical conductivity and excellent structural robustness.Consequently,the resultant Se-O-PCS hybrid is endowed with an obviously enhanced K-ions storage property.

Highly Reversible Li–Se Batteries with Ultra-Lightweight N,S-Codoped Graphene Blocking Layer

The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we present a simple vacuum filtration method to synthesize nitrogen and sulfur codoped graphene(N,S-G) blocking layer, which is ultra-lightweight, conductive, and free standing. When the N,S-G membrane was inserted between the catholyte and separator, the lithium–selenium(Li–Se)batteries exhibited a high reversible discharge capacity of 330.7 mAh g^(-1) at 1 C(1 C = 675 mA g^(-1)) after 500 cycles and high rate performance(over 310 mAh g^(-1) at 4 C) even at an active material loading as high as ～5 mg cm^(-2). This excellent performance can be ascribed to homogenous dispersion of the liquid active material in the electrode, good Li^+-ion conductivity, fast electronic transport in the conductive graphene framework, andstrong chemical confinement of polyselenides by nitrogen and sulfur atoms. More importantly, it is a promising strategy for enhancing the energy density of Li–Se batteries by using the catholyte with a lightweight heteroatom doping carbon matrix.

Design strategies of performance-enhanced Se cathodes for Li-Se batteries and beyond

Lithium-selenium(Li-Se)batteries are deemed as an emerging high energy density electrochemical energy storage system owing to their high specific capacity and volume capacity.Prior to their practicality,a series of critical challenges from the Se cathode side need to be overcome including low reactivity of bulk Se,shuttle effect of intermediates,sluggish redox kinetics of polyselenides,and volume change etc.In this review,recent progress on design strategies of functional Se cathodes are comprehensively summarized and discussed.Following the significance and key challenges,various efficient functionalized strategies for Se cathodes are presented,encompassing covalent bonding,nanostructure construction,heteroatom doping,component hybridization,and solid solution formation.Specially,the universality of these functional strategies are successfully extended into Na-Se batteries,K-Se batteries,and Mg-Se batteries.At last,a brief summary is made and some perspectives are offered with the goal of guiding future research advances and further exploration of these strategies.

Hollow Nanocages of Ni_(x)Co_(1-x)Se for Efficient Zinc–Air Batteries and Overall Water Splitting

Developing Earth-abundant,highly efficient,and anticorrosion electrocatalysts to boost the oxygen evolution reaction(OER),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER) for the Zn–air battery(ZAB) and for overall water splitting is imperative.In this study,a novel process starting with Cu2O cubes was developed to fabricate hollow NixCo1-xSe nanocages as trifunctional electrocatalysts for the OER,ORR,and HER and a reasonable formation mechanism was proposed.The Ni0.2Co0.8Se nanocages exhibited higher OER activity than its counterparts with the low overpotential of 280 mV at 10 mA cm-2.It also outperformed the other samples in the HER test with a low overpotential of 73 mV at 10 mA cm-2.As an air–cathode of a self-assembled rechargeable ZAB,it exhibited good performance,such as an ultralong cycling lifetime of > 50 h,a high round-trip efficiency of 60.86%,and a high power density of 223.5 mW cm-2.For the application in self-made all-solid-state ZAB,it also demonstrated excellent performance with a power density of 41.03 mW cm-2 and an open-circuit voltage of 1.428 V.In addition,Ni0.2Co0.8Se nanocages had superior performance in a practical overall water splitting,in which only 1.592 V was needed to achieve a current density of 10 mA cm-2.These results show that hollow NixCo1-xSe nanocages with an optimized Ni-to-Co ratio are a promising cost-effective and high-efficiency electrocatalyst for ZABs and overall water splitting in alkaline solutions.

Interface effect on promoting reversible conversion for Na2Se in the metal selenide as sodium ion batteries

The rapid development of modern electronic devices has promoted more research in the field of high energy-density storage devices[1].Lithium ion batteries(LIBs)have been widely used in electronic devices and hybrid electric vehicles since their successful commercialization by Sony[2,3].

Ni0.85 Se hexagonal nanosheets as an advanced conversion cathode for Mg secondary batteries

Mg secondary batteries are promising scalable secondary batteries for next-generation energy storage.However,Mg-storage cathode materials are greatly demanded to construct high-performance Mg batteries.Electrochemical conversion reaction provides plenty of cathode options,and strategy for cathode selection and performance optimization is of special significance.In this work,Ni0.85Se with nanostructures of dispersive hexagonal nanosheets(D-Ni0.85Se)and flower-like assembled nanosheets(F-Ni0.85Se)is synthesized and investigated as Mg-storage cathodes.Compared with F-Ni0.85Se,D-Ni0.85Se delivers a higher specific capacity of 168 mAh g^-1 at 50 mA g^-1 as well as better rate performance,owing to its faster Mg^2+-diffusion and lower resistance.D-Ni0.85Se also exhibits a superior cycling stability over 500cycles.An investigation on mechanism indicates an evolution of Ni0.85Se towards NiSe with cycling,and the Mg-storage reaction occurs between NiSe and metallic Ni^0.The present work demonstrates that advanced conversion-type Mg battery cathode materials could be constructed by soft selenide anions,and the electrochemical properties could be manipulated by rational material morphology optimization.

Ether-compatible lithium sulfur batteries with robust performance via selenium doping

The increasing demand of the green energy storage system encourages us to develop a higher energy storage system to take the place of the present lithium-ion batteries with limited energy/power densities[1,2].Among the diverse candidates。

High-efficiency sodium storage of Co_(0.85)Se/WSe_(2) encapsulated in N-doped carbon polyhedron via vacancy and heterojunction engineering

With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.

Delving into the dissimilarities in electrochemical performance and underlying mechanisms for sodium and potassium ion storage in N-doped carbon-encapsulated metallic Cu_(2)Se nanocubes

The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.

Modulating Co-Co bonds average length in Co_(0.85)Se_(1-x)S_(x) to enhance conversion reaction for potassium storage

While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.

Ni/CTs改性隔膜在Na-Se电池中的应用

Na-Se电池因其较高的理论容量,被认为具有较高的研究价值.但是由于其在充放电过程中的仍存在大倍率性能弱,充放电容量低的问题.所以需要设计新的电池结构材料以解决上述问题.本文通过一步热解法利用过渡金属镍原位催化生长碳纳米管,用Ni/CTs修饰聚丙烯隔膜用于Na-Se电池中以改善其电化学性能.结果表明,使用Ni/CTs修饰的隔膜在Na-Se电池中表现出良好的循环和倍率性能.在0.2 C电流密度下循环100圈后仍有354 mAh g^(-1)的比容量,在20 C的大电流密度下仍具有213 mAh g^(-1)的比容量,并且回到1 C电流密度下仍有283.7 mAh g^(-1)的比容量.

新型二次电池Se/C复合正极材料的微波法制备及其性能研究

采用微波热复合法合成Se/C复合正极材料,并用XRD、SEM和电化学等测试手段对样品进行表征。研究表明:该正极材料具有良好的循环性能和倍率性能。在1C倍率下经过100次充放电循环放电比容量依然达到160mAh/g。科琴黑的高导电性降低了正极的阻抗,并有效的抑制了穿梭效应。

An efficient molten-salt electro-deoxidation strategy enabling fast-kinetics and long-life aluminum-selenium batteries

Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the shuttle effect of soluble intermediate product and sluggish reaction kinetics in the solid-solid conversion process during cycling.Herein,we propose an unprecedented design concept for fabricating uniform Se/C hollow microspheres with controllable morphologies through low-temperature electro-deoxidation in neutral NaCl-AlCl_(3) molten salt system.Such Se/C hollow microspheres are demonstrated to hold a favorable hollow structure for hosting Se,which can not only suppress the dissolution of soluble intermediate products into the electrolyte,thereby maintaining the structural integrity and maximizing Se utilization of the active material,but also promote the electrical/ionic conductivity,thus facilitating the rapid reaction kinetics during cycling.Accordingly,the as-prepared Se/C hollow microspheres exhibit a high reversible capacity of 720.1 mAh g^(−1)at 500 mA g^(−1).Even at the high current density of 1000 mA g^(−1),Se/C delivers a high discharge capacity of 564.0 mAh g^(−1),long-term stability over 1100 cycles and high Coulombic efficiency of 98.6%.This present work provides valuable insights into short-process recovery of advanced Se-containingmaterials and value-added utilization for energy storage.

简便的两步直接固相反应法制备N、Se共掺杂碳限域的NiSe纳米晶及其储钠性能

通过简便的两步直接固相反应,即在室温下的固相自组装反应制备Ni席夫碱配合物前驱体,然后通过高温固相热解碳化和硒化反应,原位制备了N,Se共掺杂碳限域的NiSe纳米晶复合物。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)和热重分析(TGA)等表征技术分别对其物相、形貌结构、组分和含量等进行分析,并通过循环伏安、恒电流充放电和电化学阻抗谱等方法测试其电化学储钠性能。研究结果表明,复合物中NiSe粒子的平均尺寸为100 nm,被均匀限域在N,Se共掺杂的碳基体中;得益于该结构的优势,复合物作为钠离子电池负极材料时,在0.1 A·g-1的电流密度下充放电循环100次后仍保持291 mAh·g-1的可逆充电比容量,保持了首圈充电比容量的88%。同时,在5 A·g-1的电流密度下,可逆充电比容量为197 mAh·g-1。

Fast, green microwave-assisted synthesis of single crystalline Sb_2Se_3 nanowires towards promising lithium storage

In this work, a fast(0.5 h), green microwave-assisted synthesis of single crystalline Sb_2Se_3 nanowires was developed. For the first time we demonstrated a facile solvent-mediated process, whereby intriguing nanostructures including antimony selenide(Sb_2Se_3) nanowires and selenium(Se) microrods can be achieved by merely varying the volume ratio of ethylene glycol(EG) and H_2O free from expensive chemical and additional surfactant. The achieved uniform Sb_2Se_3 nanowire is single crystalline along [001]growth direction with a diameter of 100 nm and a length up to tens of micrometers. When evaluated as an anode of lithium-ion battery, Sb_2Se_3 nanowire can deliver a high reversible capacity of 650.2 m Ah g^(-1) at 100 mA g^(-1) and a capacity retention of 63.8% after long-term 1000 cycles at 1000 mA g^(-1), as well as superior rate capability(389.5 m Ah g^(-1) at 2000 mA g^(-1)). This easy solvent-mediated microwave synthesis approach exhibits its great universe and importance towards the fabrication of high-performance metal chalcogenide electrode materials for future low-cost, large-scale energy storage systems.

Bi_2Se_3/C Nanocomposite as a New Sodium-Ion Battery Anode Material

Bi_2Se_3 was studied as a novel sodium-ion battery anode material because of its high theoretical capacity and high intrinsic conductivity. Integrated with carbon,Bi_2Se_3/C composite shows excellent cyclic performance and rate capability. For instance, the Bi_2Se_3/C anode delivers an initial capacity of 527 mAh g^(-10) at 0.1 A g^(-1) and maintains 89% of this capacity over 100 cycles. The phase change and sodium storage mechanism are also carefully investigated.

Formation of hierarchical Fe7Se8 nanorod bundles with enhanced sodium storage properties

Ordered hierarchical architectures are attractive candidates for electrochemical energy storage applications.Herein,a facile self-template strategy is applied to prepare Fe7Se8 architectures with a monolithic structure via a self-synthesized single precursor and subsequent calcination at high temperature.With the support of oleylamine,the precursor is structurally targeted to engineer the Fe7Se8 microstructure,featuring nanorod bundles arranged along the longitudinal direction.Because of their ordered hierarchical structure,the Fe7Se8 nanorod bundles deliver a high reversible capacity of 300 m Ah g^-1 at 0.5 A g^-1,along with exceptional rate capability up to 20 A g^-1 and long-term cycle life over 8000 cycles,which represents the highest stability of Fe7Se8 anodes for sodium-ion batteries reported to date.The feasibility of the present strategy to prepare metal selenide structures highlights its promising potential for the rational and effective engineering of electrode materials responsible for the electrochemical performance of energy storage systems.

利用Se-C键将硒包封于蜂窝状三维多孔炭构筑高性能锂-硒电池正极材料

锂-硒电池因其超高的体积能量密度和硒的高电导率而被认为是一种极具有发展前景的锂离子电池。然而,循环过程中电极严重的体积膨胀和多硒化物溶解,以及硒的低负载,阻碍了锂-硒电池应用的发展。解决这三个问题的一种行之有效的方法是将硒限制在具有丰富孔体积的碳基质中,并同时增强硒与碳的界面相互作用。通过将Se浸入酒石酸盐衍生的蜂窝状三维多孔炭中,合成出了一种具有Se―C键的蜂窝状三维多孔炭@硒(HPC@Se)的新型正极材料用于锂-Se电池。得到的蜂窝状三维多孔炭的孔体积可达1.794 cm^(3)g^(-1),能够均匀包封65%硒。此外,硒与碳之间的强化学键有利于稳定硒,从而进一步缓解其巨大的体积膨胀和多硒化物的溶解,还可促进循环过程中的电荷转移。该HPC@Se正极呈现出极好的循环性能和倍率性能。在0.2 C的电流密度下,经200次循环后,其比容量可保持在561 m Ahg^(-1)(为理论比容量的83%),每次循环的比容量衰减率仅为0.058%。此外,在5 C的高电流密度下,HPC@Se正极还可以达到472.8 m Ahg^(-1)的可观容量。

A review on electronically conducting polymers for lithium-sulfur battery and lithium-selenium battery:Progress and prospects

Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.

Manipulating selenium molecular configuration in N/O dual-doped porous carbon for high performance potassium-ion storage

Potassium-selenium(K-Se)batteries have attracted more and more attention because of their high theoretical specific capacity and natural abundance of K resources.However,dissolution of polyselenides,large volume expansion during cycling and low utilization of Se remain great challenges,leading to poor rate capability and cycle life.Herein,N/O dual-doped carbon nanofibers with interconnected micro/mesopores(MMCFs)are designed as hosts to manipulate Se molecular configuration for advanced flexible K-Se batteries.The micropores play a role in confining small Se molecule(Se_(2–3)),which could inhibit the formation of polyselenides and work as physical barrier to stabilize the cycle performance.While the mesopores can confine long-chain Se(Se_(4–7)),promising sufficient Se loading and contributing to higher discharge voltage of the whole Se@MMCFs composite.The N/O co-doping and the 3D interpenetrating nanostructure improve electrical conductivity and keep the structure integrity after cycling.The obtained Se_(2–3)/Se_(4–7)@MMCFs electrode exhibits an unprecedented cycle life(395 mA h g^(−1) at 1 A g^(−1) after 2000 cycles)and high specific energy density(400 Wh kg^(−1),nearly twice the specific energy density of the Se_(2–3)@MMCFs).This study offers a rational design for the realization of a high energy density and long cycle life chalcogen cathode for energy storage.